Protocol for Safe Use of Pyrophoric/Water-Reactive Reagents
I.
Overview
Pyrophoric and water-reactive materials can ignite spontaneously on contact with air, moisture
in the air, oxygen, or water and therefore must not be exposed to the atmosphere. Specific examples
of materials are given below. Failure to follow proper handling procedures outlined by the University
can result in fire or explosion, leading to serious injuries, death, and/or significant damage to facilities.
Any handling of a pyrophoric/water-reactive material is high risk and must be controlled with adequate
system design, direct supervision and training.
Researchers should not use these reagents until they have read and fully understood these
guidelines; however, reading these guidelines does not substitute for hands-on training. New users of
pyrophoric/water-reactive reagents must work under the close supervision of the PI or designated
experienced user. All experiments/procedures should be considered a two-person task and personnel
should not work alone. All labs working with these materials must have in place written standard
operating procedures (SOPs) and documented training for each person required to handle these
materials. Excellent definitions and technical guidance can be found in Aldrich Technical Bulletins AL134, AL-164, AL-195, and AL-211. (http://www.sigmaaldrich.com/chemistry/aldrich-chemistry/techbulletins.html)
II.
Definitions and Examples of Pyrophoric Materials
OSHA 1910.1200 and NFPA 45 both define a pyrophoric material as a liquid, solid, or gas that will
ignite spontaneously in air at a temperature of 130 degrees F (54.4 degrees C) or below.
49 CFR 173.124(b)(1)defines a pyrophoric material as a liquid or solid that, even in small quantities and
without an external ignition source, can ignite within five (5) minutes after coming in contact with air
when tested according to UN Manual of Tests and Criteria.
A variety of liquid, solid, and gas reagents are pyrophoric, including (but not necessarily limited to):
• Grignard Reagents: RMgX (R=alkyl or aryl, X=halogen)
• Lithium alkyls and aryls: e.g. tert-butyllithium and n-butyllithium
• Other main group organometallics and certain transition metal organometallics: e.g.
trimethylaluminum and diethylzinc
• Metal carbonyls: e.g. nickel tetracarbonyl
• Alkylmetal alkoxides or halides (dimethylaluminum chloride, diethylethoxyaluminium)
• Metal hydrides (e.g. potassium hydride, sodium hydride, lithium aluminum hydride)
• Low molecular weight alkyl phosphines and arsines: e.g. tributyl phosphine and trimethyl arsine
• White phosphorus
• Alkali metals in zerovalent form (lithium, sodium, potassium, especially sodium potassium alloy
– NaK, and even more dangerous are cesium and rubidium)
• Metal Powders (finely divided): e.g. cobalt, iron, zinc, zirconium, magnesium
• Finely divided sulfides and phosphides, such as iron sulfides (FeS, FeS2, Fe3S4), potassium
sulfide (K2S), aluminum phosphide (AlP)
• Used hydrogenation catalysts (Raney-Ni is especially hazardous due to adsorbed hydrogen)
• Copper fuel-cell catalysts (e.g. Cu/ZnO/Al2O3)
• Boranes, including monomeric or diborane, and certain of its lower alkyl derivatives (R3B)
• Silane (SiH4) and some silane derivatives
A more extensive list of pyrophoric compounds can be found in Bretherick's Handbook of Reactive
Chemical Hazards.
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III.
Hazards
Whenever possible, pyrophorics/water-reactive materials should be handled under inert
atmospheres or in such a way that rigorously excludes air/moisture since they can ignite upon contact
with air and/or water. They all tend to be toxic and many come dissolved in a flammable solvent. Other
common hazards include corrosivity, teratogenicity, water reactivity, peroxide formation, along with
damage to the liver, kidneys, and central nervous system. Personnel should always consult the MSDS,
manufacturer and EH&S for technical advice before they begin work with these materials.
A. Pyrophoric Gases:
There are several kinds of pyrophoric gases that should be included in any discussion of
pyrophoricity. Many of these are used in manufacturing microelectronics and nanomaterials
development. The example gases presented here have four things in common: 1) they ignite
readily upon exposure to air, 2) they are all nonmetallic hydrides, 3) Many chemical derivatives
of these compounds are also pyrophoric and 4) they are all highly toxic inhalation hazards.
Always consult with EH&S prior to the start of a project involving the use of highly toxic
or pyrophoric gases.
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Arsine (AsH3) - (also known as arsenic hydride) is a colorless, highly toxic gas that is heavier
than air and has a distinctive garlic-like odor. Acute exposure to the material produces rapid
intravascular hemolysis (destruction of red blood cells) and hemoglobinuria (hemoglobin in
urine), while chronic exposure can result in anemia; peripheral neuropathy; numbness, tingling,
and weakness of the extremities; and cardiovascular disease. In general, arsine will not ignite
in air unless at elevated temperatures, but it can be detonated by a suitable heat source, shock
wave, or electrostatic discharge. Arsine may also exist in other compounds and the ignition
temperature of many arsine containing compounds can be lower than that of arsine. All arsine
compounds should be considered pyrophoric until they are properly characterized.
Diborane (B2H6) - is a highly toxic, colorless gas with a repulsive but sweet odor; it is highly
reactive and flammable. Depending on the concentration and duration, inhalation exposure to
diborane can produce symptoms ranging from central nervous system depression and
fatigue/drowsiness to pulmonary edema and pulmonary hemorrhage. Diborane forms flammable
mixtures with air over a wide range (flammable limits, 0.9% and 98%) and its ignition
temperature can range between 38 °C and 52 °C (100 °F and 125 °F); spontaneous ignition can
take place at standard temperature, pressure and humidity. It reacts spontaneously with
chlorine and forms hydrides with aluminum and lithium, which may ignite spontaneously in air. It
reacts with many oxidized surfaces as a strong reducing agent, and reacts violently with
vaporizing liquid-type extinguishing agents. Diborane is most often purchased and used in the
monomeric form, borane, where it exists as a complex with solvent or another electron donor.
Hydrolysis in water generates copious amounts of hydrogen that can rapidly build up pressure
in a closed vessel.
Phosphine (PH3) - is a highly toxic colorless gas with an ignition temperature of 212 °F, often
igniting spontaneously. In addition, at elevated temperatures, phosphine decomposes, emitting
highly toxic fumes of PO, which react vigorously with oxidizing materials. It possesses the
characteristic putrefying odor of a mixture of garlic and decaying fish. Prolonged exposure to
very low concentrations will cause chronic poisoning, characterized by anemia, bronchitis,
gastro-intestinal disturbances, and visual, speech, and motor difficulties.
Silane (SiH4) - also known as silicon tetrahydride, is a colorless gas with a choking effect (putrid
odor). It can ignite in air, especially in the presence of other hydrides as impurities. However,
99.95% pure silane ignites in air unless emerging at very high gas velocities, whereas mixtures
of up to 10% silane may not ignite. Hydrogen liberated from its reaction with air (atmospheric
oxygen) often ignites explosively. Silanes react violently with chlorine and bromine. When
silane reacts with a moist medium, such as the lungs, it can form sililic acid (further reacts with
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oxygen to form silicon dioxide) which can lead to silicosis of the lungs. All silanes should be
considered pyrophoric until they are properly characterized. Halon should not be used as an
extinguishing agent on silane fires.
B. Pyrophoric Solids (metals and nonmetals):
There are numerous solids that are pyrophoric and in general, they can be divided into two
classes: 1) metals and 2) non-metals
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Nonmetals:
There are several allotropes of phosphorus (P). The two most common are white (or yellow)
phosphorus and red phosphorous. Red phosphorus is not classically considered pyrophoric;
however, red phosphorus ignites easily and produces phosphine (a pyrophoric gas) during
combustion. Additionally, when red phosphorus is heated to >260 °C, it can change allotropes
to white phosphorus. Pyrophoric (white or yellow) phosphorus is a colorless to yellow,
translucent, waxy solid. It ignites spontaneously on contact with air at or above 30 °C (86 °F).
Phosphorus is explosive when mixed with oxidizing agents. Fumes from burning phosphorus
are highly irritating but only slightly toxic except in very high concentrations. Like red
phosphorus, white phosphorus also produces phosphine during combustion. Phosphorus fires
should be drenched with water until the fire is extinguished and then covered with wet sand.
Alternatively, a dry chemical fire extinguisher can be used. The solidified phosphorus should
then be covered with wet sand, clay, or ground limestone.
Metals (including alkali group I & II metals):
Nearly all metals will burn in air under certain conditions. Some are oxidized rapidly in the
presence of air or moisture, generating sufficient heat to reach their ignition temperatures.
Others oxidize so slowly that heat generated during oxidation is dissipated before the metal
becomes hot enough to ignite. Certain metals, notably magnesium, titanium, sodium,
potassium, NaK alloys, lithium, zirconium, hafnium, calcium, plutonium, uranium, and
thorium, are referred to as combustible metals because of the ease of ignition when they reach
a high specific area ratio (thin sections, fine particles, or molten states). However, the same
metals in massive solid form are comparatively difficult to ignite.
Properties of burning metal fires can cover a wide range, such as the following: 1) Burning
titanium produces little smoke, while burning lithium smoke is dense and profuse. 2) Some
water-moistened finely divided metals, such as zirconium, burn with near explosive violence,
while the same powder wet with oil burns quiescently. 3) Sodium melts and flows while burning;
calcium does not. 4) Some metals (e.g., uranium) have a tendency to burn long after exposure
to moist air, while prolonged exposure to dry air makes it more difficult to ignite. 5) Some metals
(especially heavy metals) can be toxic or fatal if they enter the bloodstream or their smoke
fumes are inhaled. 6) A few metals, such as thorium, uranium, and plutonium, emit ionizing
radiation that can complicate fire fighting and introduce a radioactive contamination problem.
Where possible, radioactive materials should not be processed or stored with other pyrophoric
materials because of the likelihood of widespread radioactive contamination during a fire.
Since fires involving combustible metals can require techniques/materials not commonly
encountered in conventional fire -fighting operations, it is necessary for those responsible for
controlling combustible metal fires to be thoroughly trained prior to an actual fire emergency.
Metal fires should never be approached without proper protective equipment (clothing and
respirators). Always review MSDSs to understand the properties of pyrophoric solids,
conditions in which they become pyrophoric, storage and handling practices, processing
hazards, and methods of extinguishing fires involving these kinds of metals. Metal fires are best
extinguished with sand or the use of a metal fire-rated fire extinguisher.
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C. Pyrophoric Liquids:
Many of the organometallics and organometal/organometalloid hydrides listed above can come
as neat reagents or dissolved in a highly flammable solvent, for example THF, hexane, diethyl
ether, etc., which creates several other hazards to consider, such as splashing/spraying, skin
absorption (toxicity), inhalation hazards, and fire. The number of known and potential
pyrophoric liquids is too long to list; however an example list of some commonly used
organolithium compounds is shown below. Please see links below and the manufacturer’s
MSDS for guidance/information regarding the specific material that is being used.
http://www.sigmaaldrich.com/chemistry/chemistry-products.html?TablePage=16256035) and
(http://www.sigmaaldrich.com/chemistry/chemistry-products.html?TablePage=16280202)
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Examples of Alkyls
Methyllithium lithium bromide complex solution
Methyllithium solution in diethoxymethane, diethyl ether, or cumene/THF
Ethyllithium solution in benzene/cyclohexane (9:1)
Isopropyllithium solution in pentane
Butyllithium solution in hexanes, heptanes, pentane, toluene, or cyclohexane
Isobutyllithium solution in heptane
sec-Butyllithium solution in cyclohexane
tert-Butyllithium solution in heptanes or pentane
(Trimethylsilyl)methyllithium solution in pentane
Hexyllithium solution in hexane
2-(Ethylhexyl)lithium solution 30-35 wt. % in heptane
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Examples of Alkynyls
Lithium acetylide, ethylenediamine complex 90%
Lithium acetylide, ethylenediamine complex 25 wt. % slurry in toluene
Lithium (trimethylsilyl)acetylide solution in tetrahydrofuran
Lithium phenylacetylide solution in tetrahydrofuran
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Examples of Aryls
Phenyllithium solution in di-n-butyl ether
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Other Examples
2-Thienyllithium solution in tetrahydrofuran
Lithium tetramethylcyclopentadienide
Lithium pentamethylcyclopentadienide
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IV.
Controlling the Hazards
Pyrophoric and water-reactive reagents (liquids or solids) are easily manipulated under the inert
atmosphere of an efficient glove box. Therefore, it is highly recommended that reagents (liquids or
solids) be used whenever possible within the confines of the glove box or equivalent. Caution must be
exercised with contaminated glassware, wipes, spatulas, gloves, or septa from the glove box. When
possible, the contaminated equipment should be neutralized inside the glove box prior to removal.
However, if this cannot be accomplished, the equipment should be brought out of the glove box in a
container under an inert atmosphere, connected to an inert gas line, and neutralized as appropriate. If
an inert atmosphere glove box is not available and a pyrophoric reagent, such as t-butyllithium solution,
needs to be used, the solution can be transferred by either a syringe or double-tipped needle (cannula)
outside the glove box only if the transfer takes place under an inert atmosphere using proper handling
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techniques. The potential hazards/reactivity for each material must be reviewed and the appropriate
safety measures taken prior to the start of the experiment.
BEFORE working with pyrophoric/water-sensitive reagents, users must complete the following:
1) Consult with your PI to receive approval before working with highly hazardous materials.
2) Read the relevant Material Safety Data Sheets (MSDS), technical bulletins, and guidance
documents to aid in the recognition and reduction of potential hazards. The MSDS must be
reviewed before using an unfamiliar chemical and periodically as a reminder.
3) Perform a hazard analysis and identify the potential failures or weak points in your
experimental design. Be prepared to handle accidents.
4) Prepare a written Standard Operating Procedure (SOP) identifying the safety precautions
specific to the operations. All training must be documented in writing.
 Perform a “dry run” to identify and resolve possible hazards before conducting the
actual procedure.
 Identify method of transfer based on volume of material used (syringe vs. cannula)
 Users of pyrophoric materials must be trained in proper lab technique and be able to
demonstrate proficiency.
 Search for alternative materials/techniques in your experiment in order to minimize
risk and the amount of hazardous waste generated.
5) All work must be conducted in a fume hood or glove box.
6) Know the location of eyewash/shower, fire extinguishers, fire alarm pulls, and emergency
exits.
7) Do not work alone or off hours when there are few people around to help.
8) Wear the appropriate personal protective equipment.
 Use a lab coat, goggles/face shield and gloves.
9) Maintain good work practices.
 Keep combustible materials, including paper towels, wood, and plastics, away from
pyrophoric/water-reactive reagents.
 Minimize the quantity of reagents used and stored
 All syringe transfers must be performed with a needle-lock Luer syringe
 Use the smallest quantity of material practical. It is better to do multiple transfers of
small volumes rather than attempting to handle larger quantities. However, when
transferring volumes that are >50mL or that exceed 50% of the syringe, an alternate
method should be employed (e.g. use a larger syringe or perform a cannula
transfer). If cannula transfers are necessary to perform, be extremely cautious not to
overpressurize the container. A standard pressure range for a transfer with inert gas
on a vented apparatus is between 3-5 psi.
 In order to reduce the possibility of clogging during transfer of materials, use a larger
bore needle, such as a 16-18 gauge needle. Remove all excess and nonessential
chemicals and equipment from the fume hood or glove box where pyrophoric
chemicals will be used to minimize the risk of fire.
10) NEVER return excess chemical to the original container. Small amounts of impurities
introduced into the container may cause a fire or explosion.
11) All recurring minor procedural incidents, including small flash fires, must be evaluated and
managed in order to avoid any potential for major incidents. All corrective actions should
be discussed with PI (in some cases, EH&S) and documented.
A. Personal Protective Equipment (PPE)
Eye Protection:
o Chemical splash goggles or safety glasses that meet the ANSI Z.87.1 1989 standard
must be worn whenever handling pyrophoric chemicals. Ordinary prescription eye
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glasses will NOT provide adequate protection unless they also meet this standard.
When there is the potential for splashes, goggles must be worn, and when appropriate, a
face shield added.
A face shield, worn over safety eyewear, is required any time there is a risk of explosion,
large splash hazard or a highly exothermic reaction.
All manipulations of pyrophoric chemicals which pose this risk must take place in a fume
hood with the sash in the lowest feasible position. Portable shields, clamped to the
counter top, may be used if fume hood space is not available; however, EH&S must be
contacted for guidance prior to the start of the experiment.
Skin Protection:
o In general, disposable-type chemical protective gloves do not provide a robust barrier to
skin contact when working with pyrophoric materials. If the reactive material were to
ignite and spill onto the hand, nitrile or latex gloves could also ignite and contribute to
serious injury. Additionally, latex or nitrile gloves offer little to no protection against
exposure to certain carrier solvents, such as tetrahydrofuran. Overall, it is critical to
consider the physical hazard, as well as the chemical hazard when working with
pyrophoric materials. Nomex® and related aramid fiber products are excellent fire
retardant materials, but can significantly reduce dexterity. For optimal protection and
dexterity, it is recommended that fire-retardant gloves, such as a Nomex® flight glove be
worn over a glove that provides adequate protection against chemical exposures.
Please review the MSDS or contact EH&S (http://ehs.wustl.edu ) for advice on
appropriate gloves before handling materials.
o A flame-resistant laboratory coat or coveralls should be worn when using pyrophoric
reagents. Flame -resistant materials such as flame-retardant treated cotton and
Nomex® provide thermal protection. They can ignite but will not continue to burn after
the ignition source is removed. Flame-resistant clothing should meet the American
Society for Testing and Materials standard, ASTM F2302: Standard Performance
Specification for Labeling Protective Clothing as Heat and Flame Resistant. Flameresistant clothing can be purchased from many lab supply companies, including Fisher
Safety and Lab Safety Supply. Synthetic clothing (made from synthetic polymers) is
strongly discouraged, because it is often highly flammable.
o Appropriate shoes that cover the entire foot (closed toe, closed heel, no holes in the top)
must be worn at all times. For optimal protection, we strongly recommend the use of
leather shoes.
B. Safety Equipment
Fire extinguishers:
The recommended fire extinguisher is a standard combustible metals (D) type. DO NOT use a
carbon dioxide, Halon, or water-based fire extinguisher to extinguish a pyrophoric material fire
as these types of extinguishers can exacerbate the fire in certain scenarios. In addition to the
appropriate fire extinguisher, a container of dry sand or soda ash (lime) should be kept in the
work area to extinguish any small fire that occurs, such as at the syringe tip and to receive any
last drops of reagent from the syringe and also as a general absorbent. All fire extinguishers in
the laboratory and common rooms must be checked monthly by laboratory personnel or a
departmental designee and class D (combustible metals) signs must be present to indicate the
location of this fire extinguisher type. Please review the policy on testing emergency equipment.
http://ehs.wustl.edu/resources/EHS%20Documents/Emergency_Equipment_Testing.pdf
Suitable types of class D fire extinguishers:
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Sodium chloride works well for metal fires involving magnesium, sodium, potassium,
sodium/potassium alloys, uranium and powdered aluminum. Heat from the fire causes
the agent to cake and form a crust that excludes air and dissipates heat.
Powdered copper metal is preferred for fires involving lithium and lithium alloys.
Developed in conjunction with the U.S. Navy, it is the only known lithium fire fighting
agent which will cling to a vertical surface thus making it the preferred agent on three
dimensional and flowing fires.
Graphite-based powders are also designed for use on lithium fires. This agent can also
be effective on fires involving high-melting metals such as zirconium and titanium.
Specially- designed sodium bicarbonate-based dry agents can suppress fires with most
metal akyls and pyrophoric liquids which ignite on contact with air, such as
triethylaluminum, but do not rely on a standard BC extinguisher for this purpose.
Sodium carbonate-based dry powders can be used with most Class D fires involving
sodium, potassium or sodium/potassium alloys. This agent is recommended where
stress corrosion of stainless steel must be kept to an absolute minimum.
When in doubt, a large quantity of sand will aid in controlling or extinguishing the fire by
smothering the pyrophoric material from its supply of oxygen or moisture.
Eyewash/Safety Shower:
o A combination eyewash/safety shower should be within 10 seconds travel time of where
pyrophoric chemicals are used. Inside the laboratory is optimum. Bottle-type eyewash
stations are not sufficient. Please review the policy on testing emergency eyewash/
shower
http://ehs.wustl.edu/resources/EHS%20Documents/Emergency_Equipment_Testing.pdf.
Fume Hood:
o Verify that your fume hood has been checked within the last 12 months. Many
pyrophoric chemicals release noxious or flammable gases, and some pyrophoric
materials are stored under kerosene. These materials must always be handled in a
laboratory fume hood
http://ehs.wustl.edu/resources/EHS%20Documents/Use_of_a_Chemical_Fume_Hood.p
df .
Glove box or Glove bags:
o Glove boxes are excellent devices to control pyrophoric chemicals when inert or dry
atmospheres are required. Routine preventative maintenance should be performed to
ensure the glove box maintains the proper atmospheric conditions (i.e. check for leaks,
rips/tears, dry rot, etc.). Alternatively, glove bags are relatively cheap devices that will
allow for the safe weighing/transfer of pyrophoric materials in a protected environment.
However, they should be used inside a fume hood and they should undergo rigorous
leak testing before each experiment. Please see Aldrich technical bulletin AL-211 for
further details
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al211.Par.00
01.File.tmp/al_techbull_al211.pdf
Gas Cabinets:
o Gas cabinets, with appropriate remote sensors and fire-suppression equipment, are
required.
o Gas flow, purge and exhaust systems should have redundant controls to prevent
pyrophoric gas from igniting or exploding. All pyrophoric gases must have Restricted
Flow Orifices (RFO) installed on the cylinder in order to prevent backflow. Please
contact your gas supplier for assistance.
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Emergency back-up power should be provided for all electrical controls, alarms and
safeguards associated with the pyrophoric gas storage and process systems.
Storage and Disposal
A. Storage:
Pyrophoric/water-reactive materials must be stored in accordance with International Building
Code 2009 and local fire district requirements. Please contact EH&S for additional storage
considerations. In general:
o When possible, store pyrophoric chemicals in a rated flammables storage cabinet away
from other flammable materials. Always plan ahead to minimize the available flammable
material (i.e. solvents) in the immediate vicinity.
o When refrigeration of materials is required, materials must be stored in an approved
explosion-proof refrigerator/freezer.
o Store as recommended in the MSDS. A nitrogen-filled desiccator or glove box is
considered to be suitable storage locations for these materials.
o If pyrophoric reagents are received in specially designed shipping, storage or dispensing
containers, (such as the Aldrich Sure/Seal packaging system) ensure that the integrity of
that container is maintained.
o Ensure that sufficient protective solvent, oil, kerosene, or inert gas remains in the
container while the material is stored.
o DO NOT return excess chemical to the original container. Small amounts of impurities
introduced into the container may cause a fire or explosion.
o During storage, it is possible for sufficient solvent to evaporate that highly active
pyrophoric material crystallizes from solution (e.g. lithium aluminum hydride in THF). It
should be recognized that these situations call for particular caution if the cap should be
removed.
o For storage of excess chemical, prepare a storage vessel in the following manner:
 Select a septum that fits snugly into the neck of the vessel
 Dry any new empty containers thoroughly
 Insert septum into neck in a way that prevents atmosphere from entering the
clean, dry (or reagent-filled) flask.
 Insert a needle to vent the flask and quickly inject inert gas through a second
needle to maintain a blanket of dry inert gas above the reactive reagent.
 Once the vessel is fully purged with inert gas, remove the vent needle, then the
gas line.
o For long-term storage, the septum should be secured with a copper wire (Figure 1A).
o For extra protection a second same-sized septa can be placed over the first (Figure 1b).
o The additional use of parafilm can help to maintain the integrity of the materials during
storage.
Fig. 1A Septum wired to vessel
Revised January 2012
Fig. 1B For long-term
storage, use a second septum
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B. Disposal of Pyrophoric/ Water-Reactive Reagents:
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VI.
A container with any residue of pyrophoric materials should never be left open to the
atmosphere.
Any unused or unwanted reactive materials must be destroyed by transferring the
materials to an appropriate reaction flask for hydrolysis and/or neutralization with
adequate cooling.
The empty container should be rinsed three times with a dry, COMPATIBLE solvent; this
rinse solvent must also be neutralized or hydrolyzed. The rinse solvent must be added to
and removed from the container under an inert atmosphere.
The empty, quenched container can be placed in the broken glass container, while the
solvent rinses and water rinse should be disposed as hazardous waste and should not
be mixed with incompatible waste streams.
All consumable materials that are contaminated with pyrophoric chemicals should be
quenched and disposed of as hazardous waste.
If the lab is disposing of older, potentially dried out materials through EH&S rather than
neutralizing, the containers must be partially refilled with the original inert carrier material
so that the dried material is adequately covered (e.g. dried out LiAlH4 needing additional
THF or Lithium metal ribbons needing additional mineral oil).
Alert EH&S for any wastes contaminated by pyrophoric/water-reactive chemicals by
adding in comments during the electronic submission process.
All waste-related material should be stored appropriately (e.g. kept in the fume hood or
flammables cabinet) until it is removed by EH&S.
EH&S cannot remove materials from the lab until they have been appropriately
stabilized/quenched and deemed safe for transport. Please contact Environmental
Compliance Division Managers for guidance regarding stabilization requirements and
quenching suggestions. http://ehs.wustl.edu/hmm/Pages/default.aspx
Emergency Spill/Accident Procedures
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Shut off all ignition sources and allow spilled materials to react with atmospheric moisture.
A container of powdered lime or sand should be kept within arm’s length when working with a
pyrophoric material and it should be used to completely smother and cover any spill that occurs.
DO NOT use water to attempt to extinguish a pyrophoric material fire as it can actually enhance
the combustion of some pyrophoric materials (e.g. metal compounds).
Do not use combustible materials (paper towels) to clean up a spill, as these may increase the
risk of igniting the pyrophoric compound.
Know the location and function of all appropriate emergency equipment.
Consider purchasing a fire blanket and keeping it in the working area to quickly extinguish
flames on a person.
If anyone is exposed, or on fire, wash body with copious amounts of water and try to remove
contaminated clothing.
Depending on your location, report all spills/fires by calling 362-4357 (Medical School) or 9355555 (Danforth).
Recurring incidents should be evaluated for process improvement and hazard mitigation.
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VII.
Important Things to Remember!!!
Pyrophoric/water-reactive reagents can be handled and stored safely as long as exposure to
atmospheric oxygen and moisture is limited appropriately. All work with pyrophoric/highly-toxic gases
must be reviewed by EH&S prior to start. Some finely divided solids must be transferred under an inert
atmosphere in a glove box or glove bag, or under an inert-gas funnel. Liquids may be safely
transferred without the use of a glove box by employing techniques and equipment discussed in the
Aldrich Technical Information Bulletin AL-134. Always wear appropriate PPE. Always maintain a
clutter-free work area to reduce the risk of spills and potential fires. NEVER engage in experiments that
require the use of pyrophoric materials without the proper documented training.
Reference List:
American Chemical Society
http://portal.acs.org/portal/fileFetch/C/CNBP_024230/pdf/CNBP_024230.pdf
Department of Energy
http://www.hss.doe.gov/nuclearsafety/techstds/docs/handbook/hbk1081.html
Sigma-Aldrich
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al164.Par.0001.File.tmp/al_t
echbull_al164.pdf
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull__al195.Par.0001.File.tmp/al
_techbull__al195.pdf
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al134.Par.0001.File.tmp/al_t
echbull_al134.pdf
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al211.Par.0001.File.tmp/al_t
echbull_al211.pdf
University of California Irvine
http://www.ehs.uci.edu/programs/sop_library/
University of California Los Angeles
http://www.chemistry.ucla.edu/file-storage/publicview/pdfs/ProceduresSafeSolids.pdf
http://www.chemistry.ucla.edu/file-storage/publicview/pdfs/SOPLiquidReagents.pdf
University of California Santa Barbara
http://ehs.ucsb.edu/units/labsfty/labrsc/factsheets/Organolithium_FS34.pdf
Purdue University
http://www.purdue.edu/rem/hmm/pyrophoric_fs37.pdf
Revised January 2012
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